Manifolding transfer and method of making



Dec. 22, 1953 J. G. ZlMMERMAN 2,663,579

MANIFOLDING'TRANSFER- AND METHOD OF MAKING Filed March 17, 1948INVENTOR. JEROME G. ZIMMERMAN ATTORNEY Patented Dec. 22, 1953 UNITEDSTAT MANIFOLDING TRANSFER AND METHOD OF MAKING Jerome G. Zimmerman, WestMilton, Ohio, as-

signor to The Standard Register Company, Dayton, Ohio, a corporation ofOhio Application March 17, 1948, Serial No; 15,502

11 Claims.

back of the original or copy sheets to an adjacent sheet or onto'separate interleaved sheets. Disadvantages offemploying interleavedcarbon coated tissue. between the bond sheets in order to obtainmultiple copies is that" this increases the bulk of each set of formsand produces illegible copies in the lower forms due to spreading of theindividual typed .or written characters. The commercial objection tothese individual carbon backed forms" is. the tendencyof the pigmentedmaterial to rub off and soil the hands of operator or others who handlethe same, and also to smudge off on otherforms or correspondence whenremoving them from files or in general ofiice procedure;

It is an object of'thepresent invention to provide. transfer copyingmaterials which operate Without the transfer ofrcarbon or other deepcoloring matter, and'in such a manner that a substantially colorless orlight colored compound, but potentially'capablet of forming adark'colored sulfide derivative; is transferred from the rear surface ofthe first sheetupon which the direct impression'is made to the frontsurface of the second sheet; the'latter carries a coating containingacompound" which reacts with the transferred compound to form the saiddark c01- oredsulfide. The first sheet cannot only, mean the top sheetbut any sheet below it, the term being one of order where another sheetis being considered and the transfer is from the rear surface of onesheetto'the top surface of the next sheet; And the second sheet cannotonly mean the actual secondsheet but any sheet upon which the transferis made.

A further object of the invention is'to provide transfer surfaces orcoatings upon a sheet of writing paper havingthe advantageous featuresand inherent meritorious characteristics as herein mentioned.-

With the above primary and other incidental objects in view as will'morefully appear in the specification, theinvention intended to be protectedby Letters Patent'consists of'the advantageous features, thecomponentsof the-coating compositions; and' the mode of application and useas..hereinaftendescribed 01 illustrated in the accompanyingdrawing; oritheir 'equivalents;

Inthe accompanying drawing, which is of a diagrammatic nature,

Fig. 1 is a view of a single sheet of writing paper with the transfersurfaces or coatings applied thereto, and

Fig; 2 is a view of an assembly of superposed Writing sheets forming aset of manifold record forms.

Like parts are indicated by similar characters of reference throughout-the several views.

According. to the present invention, there is provided a set oftransfercopying materials comprisinga series of two or more sized sheets ofpaper It, on the'face or upper side of eachof which sheets is pro'videdanon-sticky, non-tacky coating 1 l which contains 'a lightcolored-Watersoluble metallic'sulfide a water-insoluble polyvalent metalsalt'of a higher carboxylic acid, the sulfide of the metal of which iscolorless, and a very small amount of water. And on the reverse surfaceof the same sheet there is a'substantially firm, non-sticky, non-tackycoating I2, which contains aleadsalt and a very small amount of water. I

To prepare the upper surface, the-sized sheet of paper It] is coatedwith an emulsion ll whose phases-are a-volatile organic water-immiscibleliquid and'water; in the later there is dissolved an alkalimetalsulfide. The emulsifying agent is a -water-insoluble polyvalentmetal salt of a higher carboxylic acidincapable of forming a darksulfideby the reaction, such as aluminum palmitate. This coated sheet is-thenpermitted todry.

To prepare the reversesurface, the sized sheet of paper illis-coatedwith-an emulsion l2 whose phases arealso a volatilewater-immiscible orgame-liquid wh-ichrnay.- bethe same as in the firstemulsion, and water. Here the emulsifying agent isawater-insolublepolyvalent metal salt of a higher carboxylic acid including such leadsalts,-although preference is given such aluminum salts; in thatsituation 'where the salt of the long chain carboxylic acid is of ametal whose'sulfideis substantially colorless, there is dissolved in theaqueous phase leadnitrate or lead acetate or other water soluble leadsalts. Higher fatty acids are the preferred higher carboxylic acidsparticular the solid, saturated higher fatty acids butresin-acids ornaphthenic acids may be used'. The thuscoated reverse side of the sheetis permitted to dry.

A suitablewayto produce these contiguous surfaces of sized papertil-,one of Whichsurfaces carries a coating- I 1 containing: alightcolored lead salt and the other" surface a'coatin'g EZ COnF taining acolorless water-soluble sulfide will now be explained. One surface of asized sheet of paper In is coated with an emulsion l I composed ofpotassium sulfide dissolved in water, carbon tetrachloride and aluminumpalmitate. The reverse side of the sheet In is coated with an emulsion12 composed of lead nitrate dissolved in water, carbon tetrachloride andaluminum palmitate. These respective emulsions do not penetrate thesized paper. These respective emul- 'sions when applied to the surfacesof the sized sheets as a thin coating dry to a thin film. The respectivefinished coated surfaces possess a fairly solid or firm condition andare not sticky or tacky. Possibly very small amounts of water may beretained or exist. It is necessary to have some water in the coatingsbecause the chemical reaction that produces the copy is brought about byionization and this is impossible without water.

The emulsions can be used interchangeably on the face and reverse sideof the paper.

The sized sheets cannot be coated simply with water-solutions of asulfide and lead salt respectively. For one thing such aqueous solutionswould be taken up by the paper, and then become dry, leaving the sulfidein a dry condition upon one surface and the lead salt in a dry conditionupon the reverse side. Dry portions of an alkali metal sulfide will notreact with dry portions of a lead salt. Moreover since the paper would,after the application of the two solutions, be wet, it would allow thetwo chemicals to react at once by penetrating into the paper, causingthe formation of a dark colored metallic sulfide, such as lead sulfide.

An example of a suitable emulsion formula in terms of proportions to beapplied as a coating 12 to one surface of the sized sheet, wherein thequantities are given in terms of percentage by weight, is as follows:

. Per cent 1. Volatile organic liquid (carbon tetrachloride) 2.Water-insoluble polyvalent metal salt of a higher fatty acid (aluminumpalmitate) 3. Water-soluble inorganic lead salt (lead nitrate) 3.8 4.Water 28.2

The immiscible liquid may be any suitable volathe organic liquid, suchas carbon tetrachloride,

benzene, toluene, etc.

The polyvalent metal salt of the higher carboxylic acid which preferablyis aluminum palmitate, but aluminum stearate, calcium-, magnesium zincstearates, and other polyvalent metallic salts of the higher fattyacids, resin acids,

or naphthenic acids may be used.

Suitable Water-soluble lead salts are lead nitrate and basic leadacetate.

If lead palmitate or lead stearate is used in place of aluminumpalmitate or other of the above polyvalent metal salts of highercarboxylic acids, the sulfide of the metal of which is colortub sized(starch) paper.

4 tion will be. However, too much will hinder the reaction between thelead salt and the soluble sulfide when the transfer is attempted. It iscustomary to dissolve the shellac in methanol 01 other solvent thereforbefore adding to the other constituents. I

An example of the other emulsion II, which is to be applied to theopposite surface of the sized sheet, will have components 1, 2 and 4supra, in that approximate ratio, but the third component will be awater-soluble sulfide, such as sodium sulfide or potassium sulfide. Thisalkali metal sulfide and the soluble lead salt are present in the ratioof their chemical equivalents.

The formula for the emulsion [2 which I prefer is composed of carbontetrachloride, aluminum palmitate, and either basic lead acetate or leadnitrate, and water. The percentage by weight of carbon tetrachlorideshould exceed that of water. he constituents should be well mixed tosecure an emulsion before the application thereof to the sized paper.The formula for the emulsion l I would have water-soluble sodium sulfideinstead of the lead acetate or the lead nitrate, and in the ratio oftheir chemical equivalents; otherwise it is the same. A somewhat greaterratio of volatile organic liquid to water is the optimum ratio.

It will be understood that if only two sheets were treated it will beunnecessary to treat the top surface of the overlying sheet with oneemulsion or the under side of the only underlying sheet with the otheremulsion. But in making up transfer paper for manifold commercial orindustrial use the conventional process would be to treat the twosurfaces of each sheet of sized paper with the two different emulsionsrespectively to form on one surface a fairly firm coating which isnon-sticky or -tacky, containing a lead salt plus a very small amount ofwater and on the reverse surface a fairly firm coating which is likewisenon-sticky or -tacky, containing a light colored water-soluble metallicsulfide, a waterinsoluble polyvalent metal salt of a higher carboxylicacid, the sulfide of the metal of which is colorless, and a very smallamount of water. The coating on the other side to which reference hasbeen made contain a metallic higher carboxylate salt which may be thelead salt or a polyvalent metallic salt, the sulfide of the metal ofwhich is colorless. If it is a lead salt of a higher carboxylic acid,then as mentioned previously no other lead salt is required.

The emulsions or dispersions herein described may be applied to variousweights and qualities of sized paper having a surface which will takeand hold the coatings; a suitable sized paper is They may be applied inany suitable manner, such as spraying, brushing, and various coatingmethods. The thickness will be governed partly by the economicalconsideration but an even, thin coating should be secured, which willdry to a thin non-sticky, nontacky film containing some water.

The present invention finds utility in the making of copies or transferswherein not alone imprints by pencil, pen and typewriter are employed,but also for use with printing telegraph machines, stencil machines, andthe like.

In the specification and claims the term higher carboxylic acids denotesany carboxylic acid of eight or more carbon atoms and preferably twelveor more. The term higher fatty acids denotes those carboxylic acidsnormally present as glycerides in fatty oils and fats. Preferably thepolyvalent metal soaps are of the higher. fatty acids, wherein fattyacids may be unsaturated as well as saturated types but the latter beingpreferred.

The expression emulsion or dispersion as employed in the specificationand in the. claims is used in a broad sense to include colloids,suspensoids, emulsions, and emulsoids. It is believed that in the typeof emulsion for. both the face and reverse side of the sheet water isthe dispersed phase, but I am not bound by this theory. This is becausethe metallic soaps employed are hydrophobic emulsifiers, which are knownto form water-in-oil emulsions. Also in both the specification andclaims the term light colored embraces white as well as the lightcolored shades unless otherwise qualified.

Wh le specific materials, proportions have been described herein, itwill be understood that various changes and modifications may be madewithout departing from the spirit and scope of the invention.Accordingly I do not intend that my invention shall be limited to suchembodiment and examples, except as hereinafter described in the appendedclaims.

I claim:

1. In manifolding, superimposed contacting sized sheets, the contactingsurfaces being provided respectively with a substantially firm,nonsticky, non-tacky coating carrying therein a Very small amount ofWater and a light colored lead salt of a higher carboxylic acid, and asubstantially firm, non-sticky, non-tacky coating carrying a lightcolored Water-soluble sulfide and a water-insoluble polyvalent metalsalt of a higher carboxylic acid the sulfide of the metal of which iscolorless, and a very small amount of water.

2. The method of forming transfer papers comprising the steps of coatingone surface of a sheet of sized paper with an emulsion containing a leadsalt of a higher carboxylic acid, a volatile water-immiscible organicliquid and a lesser amount of water, coating the reverse side of thesheet with an emulsion containing a light colored sulfide dissolved inwater, a light colored Waterinsoluble polyvalent metal salt of a highercarboxylic acid the sulfide of the metal of which is colorless, and avolatile water-immiscible organic liquid the percentage of the latter tothat of the water being substantially greater, causing the coatings todry, whereby there is left on each of the said surfaces a substantiallyfirm, non-sticky, non-tacky coating but containing a very small amountof water.

3. The method of forming transfer papers comprising the steps of coatingone surface of a sheet of sized paper with an emulsion containing a leadsalt dissolved in water, a polyvalent metal salt other than lead of ahigher carboxylic acid the sulfide of the metal of which is colorless,and a volatile organic liquid, coating the reverse side of the sheetwith an emulsion containing a light colored sulfide dissolved in water,a light colored polyvalent metal salt of a higher carboxylic acid themetal of which does not form dark colored sulfides, and a volatileorganic liquid wherein there is more organic liquid than water in eachemulsion, causing the coatings to dry, whereby there is left on each ofthe said surfaces a substantially firm, non-sticky, non-tacky coatingbut containing a very small amount of water.

4. In manifolding, superimposed contacting sized sheets, the contactingsurfaces being provided respectively with a substantially firm,nonsticky, non-tacky coating carrying therein a very :small amount ofwater, a light colored lead salt of a h a t acid an a bstan ially firm,non-stiokm f Qn-ftari k tas carr n alkali metal lfid a, ver s al ainq nfof water and an'aluminum'salt of a higher fatty acid.

5 n nan fo ns superi p sed. conta t n ed h e the onta t ng urfaces, beig o; vided, respectively with a substantially firm, nonst c v, no acky.coa n ca ryin the ein a ve small amount oi'water, bleached sneuac, a lht colored lead salt of a high]: fatty acid, and a s bs antially non-t kn0n-. a 1 y coatin carrying bleached shellac, an; alkali metal sulfide,a very small amount of'water; and an aluminum salt of a higher fatty.acid.

6. The 'method of forming tran f r papers comprising the steps ofcoating one surface of a sheet of sized paper with an emulsioncontaining a lead salt dissolved in water, an aluminum salt of a. highercarbog ylic acid and a volatile organic liquid, coating thefreversasideof the sheet, with an emulsion containing an alkali metal sulfidedissolved in water, an aluminum salt of a higher carboxylic acid and avolatile organic liquid, wherein there is more organic liquid than Waterin each emulsion, causing the coatings to dry, whereby there is left oneach of the said surfaces a substantially firm, non-sticky, non-tackycoating but containing a very small amount of water.

7. The method of forming transfer papers comprising the steps of coatingone surface of a sheet of sized paper with an emulsion containing a leadsalt dissolved in water, an aluminum salt of a higher carboxylic acid,bleached shellac, and a volatile organic liquid, coating the reverseside of the sheet with an emulsion containing an alkali metal sulfidedissolved in water, an aluminum salt of a higher carboxylic acid,bleached shellac, and a volatile organic liquid, wherein there is moreorganic liquid than water in each emulsion, causing the coatings to dry,whereby there is left on each of the said surfaces a substantially firm,non-sticky, non-tacky coating but containing a very small amount ofwater.

8. The method of forming transfer paper comprising the steps of coatingone surface of a sheet of sized paper with an emulsion containing a leadsalt of a higher fatty acid, a volatile Waterimmiscible organic liquidand a lesser amount of water compared to the organic liquid, coating thereverse side of the sheet with an emulsion containing an alkali metalsulfide dissolved in water, an aluminum salt of a higher fatty acid anda volatile water-immiscible organic liquid, the latter beingsubstantially greater than the amount of water, whereby there is left oneach of said surfaces a substantially firm, non-sticky, Eon-tackycoating, and causing said coating to 9. In manifolding, superimposedcontacting sized sheets, the contacting surfaces being providedrespectively with a substantially firm, nonsticky, non-tacky, lightcolored coating carrying therein a very small amount of water, awater-soluble lead salt, and a light colored water-insoluble polyvalentmetal salt of a higher carboxylic acid the sulfide of the metal of whichis colorless, and a, substantially firm, non-sticky, non-tacky coatingcarrying therein an alkali metal sulfide, a light coloredwater-insoluble polyvalent metal salt of a higher carboxylic acid thesulfide of the metal of which is colorless, and a very small amount ofwater.

10. In manifolding, superimposed contacting sized sheets, the contactingsurfaces being provided with a substantially firm, non-sticky,nonaeeas're tacky, light colored coating, which coating is characterizedby the presence of a higher fatty acid radical in the form of awater-insoluble salt, and lead as an element in a salt, and furthercharacterized in that when said lead is combined as a salt which iswater-soluble, the said fatty acid radical is combined as a salt of apolyvalent metal the sulfide of whose metal is colorless, and asubstantially firm, non-sticky, non-tacky light colored coatingincluding a water-soluble metallic sulfide and a polyvalent metal saltof a higher fatty acid, the sulfide of the metal of which is colorless,and a very small amount of water being present in each of the respectivecoatings.

11. In manifolding, superimposed contacting sized sheets, the contactingsurfaces being provided respectively with a substantially firm,nonsticky, non-tacky, light colored coating, which coating ischaracterized by the presence of a higher carboxylic radical in the formof a waterinsoluble salt, and lead as an element in a salt,

and further characterized in that when said lead is combined as a saltwhich is Water-soluble, the said carboxylic radical is combined as asalt of a polyvalent metal the sulfide of whose metal is colorless, anda substantially firm, non-sticky, non-tacky light colored coatingincluding a water-soluble metallic sulfide and a polyvalent metal saltof a higher carboxylic acid, the sulfide of the metal of which iscolorless, and a very small amount of water being present in each of therespective coatings.

JEROME G. ZIMMERMAN.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 1,781,902 Gill Nov. 18, 1930 1,950,982 Gookin et al Mar. 13,1934 2,083,206 Schoeller June 8, 1937

